Diaminopyrazole derivatives and dyes containing said compounds

ABSTRACT

Diaminopyrazole derivatives of the general Formula (I) or their physiological tolerated, water-soluble salts with inorganic or organic acids,                    
     and agents, containing these compounds, for the oxidative dyeing of fibers.

The invention relates to new diaminopyrazole derivatives, as well as toagents containing these compounds for dyeing keratin fibers.

In the field of dyeing keratin fibers, especially of dyeing hair,oxidation dyes have achieved appreciable importance. The dyeing takesplace here by the reaction of certain developer substances with certaincoupler substances in the presence of suitable oxidizing agents. Asdeveloper substances, especially 2,5-diaminotoluene,2,5-diaminophenylethyl alcohol, p-aminophenol and 4,5-diaminopyrazolederivatives are used and, as coupler substances, resorcinol,4-chlororesorcinol, 1-napthol, 3-aminophenol and derivates ofm-phenylenediamine may be mentioned.

Oxidation dyes, which are used to dye human hair, must satisfy numerousrequirements in addition to dyeing the hair in the desired intensity.For example, the dyes must be safe from a toxicological anddermatological point of view and the hair dyeings achieved must havegood light fastness, acid fastness and crocking fastness and notinterfere with permanent wave stability. In any case, however, suchdyeings, in the absence of the effects of light, rubbing, and chemicalagents, must remain stable for a period of at least 4 to 6 weeks. Inaddition, it is necessary that a broad palette of different colornuances can be produced by combinations of suitable developer substancesand coupler substances. Until now, to cover the increasingly importantred region, primarily 4-aminophenol was widely used as a developer. Theuse of certain diaminopyrazole derivatives in oxidation hair dyeingagents is known from the EP-OS 740 931, DE-OS-42 34 886 and EP-OS 0 786244. However, the requirements, which must be met by oxidation dyes, arenot fulfilled in every respect by these compounds. For example, thedyeings obtained in some cases do not have a satisfactory colorintensity and/or pure red shades are not obtained. There is therefore acontinued need for new developer substances which fulfill theaforementioned requirements particularly well.

For this purpose, it has now surprisingly been found that newdiaminopyrazole derivates of the general Formula (I) fulfill therequirements imposed on developer substances particularly well. Forexample, color nuances, which are exceedingly intensive, light fast andwash fast, are obtained using these developer substances with most ofthe known coupler substances.

The object of the present invention therefore are diaminopyrazolederivatives of the general formula (I) or their physiologicallytolerated, water soluble salts with inorganic or organic acids

wherein

R1 represents a C₁-C₆ alkyl group, a C₂-C₄ hydroxyalkyl group, a C₃-C₄dihydroxyalkyl group or a C₂-C₆ alkoxy (C₁-C₂) alkyl group, a phenylgroup, a benzyl group or a substituted benzyl group;

R2 and R3 independently of one another are hydrogen, a C₁-C₆ alkylgroup, a hydroxy (C₂-C₄) alkyl group, a dihydroxy (C₃-C₄) alkyl group ora C₂-C₄ alkoxy (C₁-C₂) alkyl group or R2 and R3, together with thenitrogen, form a 4-member to 8-member heteroaliphatic ring;

R4 represents hydrogen or a C₁-C₆ alkyl group;

R5 is hydrogen, a C₁-C₆ alkyl group, an unsaturated C₂-C₆ alkyl group, ahydroxy (C₂-C₄) alkyl group, a dihydroxy (C₃-C₄) alkyl group, an amino(C₂-C₄) alkyl group, a dimethylamino (C₂-C₄) alkyl group, an acetylamino(C₂-C₄) alkyl group, a methoxy (C₂-C₄) alkyl group, an ethoxy (C₂-C₄)alkyl group, a C₁-C₄ cyanoalkyl group, a carboxy (C₁-C₄) alkyl group oran aminocarbonyl (C₁-C₄) alkyl group;

R6, R7, R8, R9, R10 independently of one another represent hydrogen, ahalogen atom (F, Cl, Br, I), a cyano group, a hydroxy group, a C₁-C₄alkoxy group, a hydroxy (C₂-C₄) alkoxy group, a C₁-C₆ alkyl group, aC₁-C₄ alkylthioether group, a mercapto group, a nitro group, an aminogroup, a (C₁-C₄) alkylamino group, a hydroxy (C₂-C₄) alkylamino group, adi(C₁-C₄) alkylamino group, a di(hydroxy(C₂-C₄)alkyl) amino group, a(dihydroxy(C₃-C₄)alkyl) amino group, a(hydroxy(C₂-C₄)alkyl)-(C₁-C₄)alkylamino group, a trifluoromethyl group,a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃ group, an —Si(CH₃)₃ group,a hydroxy(C₂-C₄) alkyl group or a dihydroxy(C₃-C₄) alkyl group or twoadjacent R6 to R10 groups form an —O—CH2—O— bond.

As compounds of Formula (I), the following may be mentioned by way ofexample:

2-isopropyl-5-phenylaminomethyl-2H-pyrazole-3,4-diamine,4-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenol,3-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenol,5-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-2-methyl-phenol,5[(3,4-dimethoxy-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,2-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-4-nitro-phenol,5-[(3-amino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,5-[(4-amino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,5[(4-amino-2 or3-methyl-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine, 2-{5or 6-amino-2 or3-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenyl}-ethanol,2-{4-amino-2-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenoxy}-ethanol,5-[(4-dimethylamino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,2-{4,5-diamino-3-[(3-amino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-{4,5-diamino-3-[(4-amino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-{4,5-diamino-3-[(4-amino-2-methyl-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-(4,5-diamino-3-{[4-amino-2-(2-hydroxy-ethyl)-phenylamino]-methyl}-pyrazole-1-yl)-ethanol,2-{4,5-diamino-3-[(4-dimethylamino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-[4,5-diamino-3-(benzo[1,3]dioxol-5-yl-aminomethyl)-pyrazole-1-yl]ethanol,4-chloro-2-{[4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol,2-(4,5-diamino-3-phenylaminomethyl-pyrazole-1-yl)-ethanol,4-{[4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole-3-ylmethyl]-amino}phenol,3-{[4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol,5-{[4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole-3-ylmethyl]-amino}-2-methyl-phenol,2-{[4,5-diamino-3-[(3,4-dimethoxy-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-{[4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole-3-ylmethyl]-amino}-4-nitro-phenol,2-(4-methyl-benzyl)-5-phenylaminomethyl-2H-pyrazole-3,4-diamine,2-benzyl-5-phenylaminomethyl-2H-pyrazole-3,4-diamine,2-methyl-5-phenylaminomethyl-2H-pyrazole-3,4-diamine,2-phenyl-5-phenylaminomethyl-2H-pyrazole-3,4-diamine,2-t-butyl-5-phenyl-aminomethyl-2H-pyrazole-3,4-diamine,5-[(4-amino-phenylamino)-methyl]-2-(4-methyl-benzyl)-2H-pyrazole-3,4-diamine,5-[(4-amino-phenylamino)-methyl]-2-benzyl-2H-pyrazole-3,4-diamine,4-[(4,5-diamino-1-(4-methyl-benzyl)-1H-pyrazole-3-ylmethyl)-amino]phenol,4-[(4,5-diamino-1-benzyl-1H-pyrazole-3-ylmethyl)-amino]-phenol.

Preferred are compounds of Formula (I), in which (i) R2 and R3 representhydrogen and R1 represents a C₁-C₄ alkyl group, a C₂-C₄ hydroxyalkylgroup, a benzyl group or a methylbenzyl group and/or (ii) R2, R3, R4 andR5 represent hydrogen and R1 represents a C₁-C₄ alkyl group, a C₂-C₄hydroxyalkyl group, a benzyl group or a methylbenzyl group, and/or (iii)R2, R3, R4 and R5 represent hydrogen and R1 represents a C₁-C₄ alkylgroup, a C₂-C₄ hydroxyalkyl group, a benzyl group or a methylbenzylgroup, and at least one of the R6 to R10 groups is a hydroxy group or anamino group, while the remaining R6 to R10 groups are hydrogen.

In particular, the following compounds or their salts with inorganic ororganic acids may be mentioned:

4-{[4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol,2-{4,5-diamino-3-[(4-amino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-(4,5-diamino-3-phenylaminomethyl-pyrazole-1-yl)-ethanol,2-isopropyl-5-phenylaminomethyl-2H-pyrazole-3,4-diamine,2-{4,5-diamino-3-[(3-amino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-{4,5-diamino-3-[(4-amino-2-methyl-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-{4,5-diamino-3-[(4-amino-3-methyl-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-(4,5-diamino-3-{[4-amino-2-(2-hydroxyethyl)-phenylamino]-methyl}-pyrazole-1-yl)-ethanol,2-(4,5-diamino-3-{[4-amino-3-(2-hydroxyethyl)-phenylamino]-methyl}-pyrazole-1-yl)-ethanol,2-{4,5-diamino-3-[(4-dimethylamino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-[4,5-diamino-3-(benzo[1,3]dioxol-5-ylaminomethyl)-pyrazole-1-yl]-ethanol,4-chloro-2-{[4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol,3-{[4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol,5-{[4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}-2-methyl-phenol,2-{4,5-diamino-3-[(3,4-dimethoxy-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-{[4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole-3-ylmethyl]-amino}-4-nitro-phenol,4-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenol,3-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenol,5-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-2-methyl-phenol,5-[(3,4-dimethoxy-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,2-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-4-nitro-phenol,5-[(3-amino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,5-[(4-amino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,5-[(4-amino-2-methyl-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,5-[(4-amino-3-methyl-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,2-{5-amino-2-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenyl}-ethanol,2-{6-amino-3-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenyl}-ethanol,2-{4-amino-2-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenoxy}-ethanoland5-[(4-dimethylamino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine.

The compounds of Formula (I) may be used as free bases, as well as inthe form of their physiologically tolerated salts with inorganic ororganic acids, such as hydrochloric acid, sulfuric acid, phosphoricacid, acetic acid, propionic acid, lactic acid or citric acid.

The inventive diaminobenzene derivatives of Formula (I) can besynthesized using known methods. The inventive compounds can besynthesized, for example, by a reductive amination of a substitutedpyrazole of Formula (II)

with an amine of Formula (III)

in which

Ra represents a protective group, as described, for example, in thechapter “Protective groups” in Organic Synthesis, Chapter 7, WileyInterscience, 1991,

Rb represents NR2Ra or NR2R3,

and the R1 to R10 groups have the meanings given in Formula (I), theprotective group subsequently being split off.

The inventive diaminopyrazole derivatives of Formula (I) are readilysoluble in water and make possible dyeings with a high color intensityand excellent color fastness, especially as far as the light fastness,wash fastness and resistance to crocking are concerned. Furthermore, thecompounds of Formula (I) furthermore have an excellent shelf life,particularly as components of the dyeing agents described below.

A further object of the present invention therefore are agents for theoxidative dyeing of keratin fibers, such as hair, fur, feathers or wool,especially human hair, on the basis of a combination of developer andcoupler substances, which contain, as developer substance, at least onediaminopyrazole derivative of Formula (I).

The diaminopyrazole derivative of Formula (I) is contained in theinventive dyeing agent in an amount of about 0.005 to 20 percent byweight, an amount of 0.01 to 5 percent by weight and especially of 0.15o 2.5 percent by weight being preferred.

As coupler substances, preferably N-(3-dimethylamino-phenyl)-urea,2,6-diamino-pyridine, 2-amino-4-[(2-hydroxyethyl)-amino]-anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxy-ethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxy-pyridine,3-amino-6-methoxy-2-(methylamino)-pyridine,2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene,2,4-diamino-1-(3-hydroxy-propoxy)-benzene,2,4-diamino-1-(3-methoxypropoxy)-benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[(di(s-hydroxy-ethyl)amino]-aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene, 5-methyl-2-(1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline,3-[(2-aminoethyl)-amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane,di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole,3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol,5-amino-4-fluoro-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol,5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichloro-phenol,3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol,3-amino-phenol, 2-[(3-hydroxyphenyl)-amino]-acetamide,5-[(2-hydroxy-ethyl)amino]-2-methyl-phenol,3-[(2-hydroxy-ethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol,5-amino-2-ethyl-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol,5-[(3-hydroxypropyl)amino]-2-methyl-phenol,3-[(2,3-dihydroxypropyl)-amino]-2-methyl-phenol,3-[(2-hydroxyethyl)-amino]-2-methyl-phenol, 2-amino-3-hydroxy-pyridine,5-amino-4-chloro-2-methyl-phenol, 1-naphthol, 1,5-dihydroxy-naphthalene,1,7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene,2,7-dihydroxy-naphthalene, 2-methyl-1-naphthol-acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,1,3-dihydroxy-2,4-dimethylbenzene, 3,4-methylenedioxy-phenol,3,4-methylenedioxy-aniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxol,6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diamino-benzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 4-hydroxy-indole,5-hydroxy-indole, 6-hydroxy-indole, 7-hydroxy-indole and2,3-indolindione, or their salts come into consideration.

Although the advantageous properties of the diaminopyrazole derivativesof the general Formula (I), which are described here, suggest that thesebe used as the only developer substance, it is, of course, also possibleto use the diaminopyrazole derivatives of the general Formula (I)together with known developer substances, such as 1,4-diaminobenzene(p-phenylenediamine), 1,4-diamino-2-methylbenzene (p-toluylenediamine),1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene,1,4-diamino-2,3-dimethylbenzene, 2-chloro-1,4-diaminobenzene,4-phenylamino-aniline, 4-dimethylamino-aniline, 4-diethylamino-aniline,4-[di(2-hydroxyethyl)amino]-aniline, 4-[(2-methoxyethyl)amino]-aniline,4-[(3-hydroxypropyl)amino]-aniline,1,4-diamino-2-(2-hydroxyethyl)-benzene,1,4-diamino-2-(1-hydroxyethyl)-benzene,1,4-diamino-2-(1-methylethyl)-benzene,1,3-bis[(4-aminophenyl)-(2-hydroxyethyl)amino]-2-propanol,1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-amino-phenol,4-amino-3-methyl-phenol, 4-methylamino-phenol,4-amino-2-(aminomethyl)-phenol,4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol,4-amino-2-(methoxy-methyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol,5-amino-salicylic acid, 2,5-diamino-pyridine,2,4,5,6-tetraamino-pyrimidine, 2,5,6-triamino-4-(1H)-pyrimidone,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-[(4-methyl-phenyl)methyl]-1H-pyrazole,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,4,5-diamino-1-methyl-1H-pyrazole,4,5-diamino-3-methyl-1-phenyl-1H-pyrazole,4,5-diamino-1-(2-hydroxyethyl)-3-methyl-1H-pyrazole, 2-amino-phenol,2-amino-6-methyl-phenol and 2-amino-5-methyl-phenol or their salts.

The coupler and developer substances may be contained in the inventivedyeing agents by themselves or in admixture with one another, the totalamount of coupler substances and of developer substances in theinventive dyeing agent (based on the total amount of the dyeing agent)in each case being 0.005 to 20 percent by weight, preferably about 0.01to 5 percent by weight and particularly 0.1 to 2.5 percent by weight.

The total amount of the combination of the developer and couplersubstances, contained in the dyeing agent described here, preferably isabout 0.01 to 20 percent by weight, an amount of about 0.02 to 10percent by weight and, in particular, 0.2 to 6 percent by weight beingparticularly preferred. The developer substances and coupler substancesare generally used in about equimolar amounts; however, it is not,however, disadvantageous if the developer substances or the couplersubstances are present in this regard in a certain excess.

Moreover, the inventive dyeing agent may additionally contain other dyecomponents, such as 6-amino-2-methylphenol and 2-amino-5-methylphenol.

The compounds of Formula (I) can of course also be used in combinationwith conventional substantive anionic, cationic, zwitterionic ornonionic dyes. The preferred anionic dyes include, for example,6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalene disodium sulfonate(CI15985; Food Yellow No. 3; FD&C Yellow No. 6),2,4-dinitro-1-naphthol-7-disodium sulfonate (CI10316; Acid Yellow No. 1;Food Yellow No. 1), 2-(indane-1,3-dione-2-yl)quinoline-x,x-sulfonate(mixture of mono and disulfonate) (CI47005; D&C Yellow No. 10; FoodYellow No. 13, Acid Yellow No. 3),5-hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo]-pyrazole-3-trisodiumcarbonate (CI19140; Food Yellow No. 4; Acid Yellow No. 23),9-(2-carboxyphenyl)-6-hydroxy-3H-xanthene-3-one (CI45350; Acid YellowNo. 73; D&C Yellow No. 8),5-[(2,4-dinitro-phenyl)amino]-2-phenylamino-sodium benzenesulfonate(CI10385; Acid Orange No. 3), 4-[(2,4-dihydroxyphenyl)azo]-monosodiumbenzenesulfonate (CI14270; Acid Orange No. 6),4-[(2-hydroxynaphth-1-yl)azo]-sodium benzenesulfonate (CI15510; AcidOrange No. 7),4-[(2,4-dihydroxy-3-[(2,4-dimethylphenyl)azo]phenyl)azo]-sodiumbenzenesulfonate (CI20170; Acid Orange No. 24),4-hydroxy-3-[(4-sulfonaphth-1-yl)azo]-1-naphthalene-disodium sulfonate(CI14720; Acid Red No. 14),6-hydroxy-5-[(4-sulfonaphth-1-yl)azo]-2,4-naphthalene-trisodiumdisulfonate (CI16255; Ponceau 4R; Acid Red No. 18),3-hydroxy-4-[(4-sulfonaphth-1-yl)azo]-2,7-naphthalene-trisodiumdisulfonate (CI16185; Acid Red No. 27),8-amino-1-hydroxy-2-(phenylazo)-3,6-naphthalene-disodium disulfonate(CI17200; Acid Red No. 33),5-(acetylamino)-4-hydroxy-3-[(2-methylphenyl)-azo]-2,7-naphthalene-disodiumdisulfonate (CI18065; Acid Red No. 35),2-(3-hydroxy-2,4,5,7-tetraiod-dibenzopyran-6-one-9-yl)-disodium benzoicacid (CI45430; Acid Red No. 51), the internal salt ofN-[6-(diethylamino)-9-(2,4-disulfophenyl)-3H-xanthene-3-ylidene]-N-ethylethaneaminium hydroxide, sodium (CI45100; Acid Red No. 52),8-[(4-(phenylazo)-phenyl)azo]-7-naphthol-1,3-disodium disulfonate(CI27290; Acid Red No. 73),2′,4′,5′,7′-tetrabromo-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),9′-[9H]xanthene]-3-one-disodium(CI45380; Acid Red No. 87),2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachloro-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),9′[9H]xanthene]-3-one-disodium(CI45410; Acid Red N. 92),3′,6′-dihydroxy-4′,5′-diiodospiro-[isobenzofuran-1(3H),9′(9H)-xanthene)-3-one-disodium(CI45425; Acid Red No. 95),(2-sulfophenyl)di[4-(ethyl((4-sulfophenyl)methyl)amino)-phenyl]-carbenium-disodium,betaine (CI42090; Acid Blue No. 9; FD&C Blue No. 1),1,4-bis[(2-sulfo-4-methylphenyl)amino]-9,10-anthraquinone-disodium(CI61570; Acid Green No. 25), the internal salt ofbis[4-(dimethylamino)-phenyl]-(3,7-disulfo-2-hydroxy-naphth-1-yl)carbenium,monosodium (CI44090; Food Green No. 4; Acid Green No. 50), the internalsalt of bis[4-(diethylamino)phenyl](2,4-disulfophenyl)-carbenium, sodium(2:1) (CI42045; Food Blue No. 3; Acid Blue No. 1), the internal salt ofbis[4-(diethylamino)phenyl](5-hydroxy-2,4-disulfophenyl)-carbenium,calcium salt (2:1) (CI42051; Acid Blue No. 3),1-amino-4-(cyclohexylamino)-9,10-anthraquinone-2-sodium sulfonate(CI62045; Acid Blue No. 62),2-(1,3-dihydro-3-oxo-5-sulfo-2H-indole-2-ylidene)-2,3-dihydro-3-oxo-1H-indole-5-disodiumsulfonate (CI73015; Acid Blue No. 74), the internal salt of9-(2-carboxyphenyl)-3-[(2-methylphenyl)-amino]-6-[(2-methyl-4-sulfophenyl)amino]xanthylium,monosodium (CI45190; Acid Violet No. 9),1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone sodium(CI60730; D&C Violet No. 2; Acid Violet No. 43),bis[3-nitro-4-[(4-phenylamino)-3-sulfo-phenylamino]-phenyl]-sulfone(CI10410; Acid Brown No. 13),5-amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)-2,7-naphthalenedisodium disulfonate (CI20470; Acid Black No. 1),3-hydroxy-4-[(2-hydroxynaphth-1-yl)azo]-7-nitro-1-naphthalene sulfonatechromium complex (3:2) (CI15711; Acid Black No. 52),3-[(2,4-dimethyl-5-sulfophenyl)azo]-4-hydroxy-1-naphthalene disodiumsulfonate (CI14700; Food Red No. 1; Ponceau SX; FD&C Red No. 4),4-(acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-sulfophenyl)azo]naphth-1-yl)azo]-1,7-naphthalenetetrasodium disulfonate (CI28440; Food Black No. 1) and3-hydroxy-4-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazole-4-ylazo)-naphthalene-1-sodiumsulfonate chromium complex (Acid Red No. 195).

The preferred cationic dyes include, for example,9-(dimethylamino)-benzo[a]phenoxazine-7-ium-chloride (CI51175; BasicBlue No. 6), di[4-(diethylamino)phenyl][4-(ethylamino)naphthyl]carbeniumchloride (CI42595; Basic Blue No. 7),3,7-di(dimethylamino)phenothiazine-5-ium-chloride (CI52015; Basic BlueNo. 9),di[4-(dimethylamino)phenyl][4-(phenylamino)naphthyl]carbenium-chloride(CI44045; Basic Blue No. 26),2-[(4-(ethyl(2-hydroxyethyl)amino)phenyl)azo]-6-methoxy-3-methyl-benzothiazolium-methylsulfate(CI11154; Basic Blue No. 41),8-amino-2-bromo-5-hydroxy-4-imino-6-[(3-(trimethylammonio)phenyl)amino]-1(4H)-naphthalenonechloride (CI56059; Basic Blue No. 99),bis[4-(dimethylamino)-phenyl][4-(methylamino)phenyl]carbenium chloride(CI42535; Basic Violet No. 1), tris(4-amino-3-methylphenyl)-carbeniumchloride (CI42520; Basic Violet No. 2),tris[4-(dimethylamino)phenyl]carbenium-chloride (CI42555; Basic VioletNo. 3), 2-[3,6-(diethylamino)dibenzopyranium-9-yl]-benzoic acid chloride(CI45170; Basic Violet No. 10),di(4-aminophenyl)(4-amino-3-methylphenyl)carbenium-chloride (CI42510;Basic Violet No. 14),1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene (CI21010; BasicBrown No. 4),1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol-chloride(CI12250; Basic Brown No. 16),1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol-chloride(CI12251; Basic Brown No. 17),1-[(4-amino-3-nitro-phenyl)azo]-7-(trimethylammonio)-2-naphthol-chloride(CI12251; Basic Brown No. 17),3,7-diamino-2,8-dimethyl-5-phenyl-phenazinium-chloride (CI50240; BasicRed No. 2),1,4-dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1,2,4-triazolium-chloride(CI11055; Basic Red No. 22),2-hydroxy-1-[(2-methoxy-phenyl)azo]-7-(trimethylammonio)-naphthalene-chloride(CI12245; Basic Red No. 76),2-[2-((2,4-dimethoxy-phenyl)amino)ethenyl]-1,3,3-trimethyl-3H-indole-1-ium-chloride(CI48055; Basic Yellow No. 11),3-methyl-1-phenyl-4-[(3-(trimethylammonio)phenyl)-azo]-pyrazole-5-one-chloride(CI12719; Basic Yellow No. 57) andbis[4-(diethylamino)phenyl]phenylcarbenium-hydrogen sulfate (1:1)(CI42040; Basic Green No. 1).

As suitable nonionic dye (especially to improve color leveling and toproduce special nuances), the following may be mentioned, for example:1-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5),1-(2-hydroxyethoxy)-2-[(2-hydroxyethyl)-amino]-5-nitrobenzene (HC YellowNo. 4), 1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Yellow No. 2),2-[(2-hydroxyethyl)amino]-1-methoxy-5-nitrobenzene,2-amino-3-nitro-phenol,1-(2-hydroxyethoxy)-3-methylamino-4-nitrobenzene,2,3-(dihydroxy-propoxy)-3-methylamino-4-nitrobenzene,2-[(2-hydroxyethyl)amino]-5-nitrophenol (HC Yellow No. 11),3-[(2-amino-ethyl)amino]-1-methoxy-4-nitrobenzene-hydrochloride (HCYellow No. 9), 1-[(2-ureidoethyl)amino]-4-nitrobenzene,4-[(2,3-dihydroxypropyl)amino]-3-nitro-1-trifluoromethylbenzene (HCYellow No. 6), 1-chloro-2,4-bis-[(2-hydroxyethyl)amino]-5-nitrobenzene(HC Yellow No. 10), 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-chloro-4-[(2-hydroxyethyl)amino]-3-nitrobenzene (HC Yellow No. 12),4-[(2-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene (HC YellowNo. 13), 4-[(2-hydroxyethyl)-amino]-3-nitrobenzonitrile (HC Yellow No.14), 4-[(2-hydroxyethyl)amino]-3-nitro-benzamide (HC Yellow No. 15),1-amino-4-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 7),2-amino-4,6-dinitro-phenol, 2-ethylamino-4,6-dinitrophenol,4-amino-2-nitro-diphenylamine (HC Red No. 1),1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene-hydrochloride (HC RedNo. 13), 1-amino-5-chloro-4-[(2-hydroxyethyl)amino]-2-nitrobenzene,4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3),4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)-amino]-3-nitrophenol,1-[(2-aminoethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzene (HC OrangeNo. 2),4-(2,3-dihydroxy-propoxy)-1-[(2-hydroxy-ethyl)armino]-2-nitrobenzene (HCOrange No. 3),1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC RedNo. 10), 5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HCRed No. 11), 2-[(2-hydroxyethyl)amino]-4,6-dinitro-phenol,4-ethylamino-3-nitrobenzoic acid,2-[(4-amino-2-nitrophenyl)amino]-benzoic acid,2-chloro-6-methylamino-4-nitrophenol,2-chloro-6-[(2-hydroxyethyl)amino]-4-nitrophenol,2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol,4-[(3-hydroxypropyl)amino]-3-nitrophenol, 2,5-diamino-6-nitropyridine,1,2,3,4-tetrahydro-6-nitroquinoxaline,7-amino-3,4-dihydro-6-nitro-2H-1,4-benzooxazine (HC Red No. 14),1,4-bis[(2-hydroxyethyl)amino]-2-nitrobenzene,1-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]-benzene (HCBlue No. 2), 1-amino-3-methyl-4-[(2-hydroxyethyl)amino]-6-nitrobenzene(HC Violet No. 1),4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene-hydrochloride(HC Blue No. 12),4-[di(2-hydroxyethyl)amino]-1-[(2-methoxyethyl)amino]-2-nitrobenzene (HCBlue No. 11),1-[(2,3-dihydroxy-propyl)amino]-4-[methyl-(2-hydroxyethyl)-amino]-2-nitrobenzene(HC Blue No. 10),1-[(2,3-dihydroxypropyl)amino]-4-[ethyl-(2-hydroxyethyl)amino]-2-nitrobenzene-hydrochloride(HC Blue No. 9),1-(3-hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene (HCViolet No. 2),1-methylamino-4-[methyl-(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HCBlue No. 6), 2-((4-amino-2-nitrophenyl)amino)-5-dimethyl-amino-benzoicacid (HC Blue No. 13),1,4-di[(2,3-dihydroxypropyl)amino]-9,10-anthraquinone,1-[(2-hydroxyethyl)amino]-4-methylamino-9,10-anthraquinone (CI61505,Disperse Blue No. 3), 2-[(2-aminoethyl)amino]-9,10-anthraquinone (HCOrange No. 5),1-hydroxy-4-[(4-methyl-2-sulfo-phenyl)amino]-9,10-anthraquinone,1-[(3-aminopropyl)amino]-4-methyl-amino-9,10-anthraquinone (HC Blue No.8), 1-[(3-aminopropyl)amino]-9,10-anthraquinone (HC Red No. 8),1,4-diamino-2-methoxy-9,10-anthraquinone (CI62015, Disperse Red No. 11,Solvent Violet No. 26),1,4-dihydroxy-5,8-bis[(2-hydroxyethyl)amino]-9,10-anthraquinone(CI62500, Disperse Blue No. 7, Solvent Blue No. 69),1-[di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]-benzene(CI11210, Disperse Red No. 17),4-[(4-amino-phenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzene (HCYellow No. 7), 2,6-diamino-3-[(pyridine-3-yl)azo]-pyridine,2-((4-(acetylamino)phenyl)-azo)-4-methylphenol (CI11855; Disperse YellowNo. 3).

Of the group of substantive dyes, the following are mentionedespecially: 2-amino-4,6-dinitrophenol, 2-ethylamino-4,6-dinitrophenyl,2-((2-hydroxy-ethyl)amino)-4,6-dinitrophenol and dyes of the generalformula (IV)

in which R is hydrogen, methyl, ethyl, or hydroxymethyl.

The total concentration of substantive dye in the inventive agent isabout 0.1 to 10 percent by weight and preferably 0.1 to 5 percent byweight.

Of course, if the coupler and developer substances, as well as the othercomponents of the dye are bases, they can also be used in the form oftheir physiologically tolerated salts with organic or inorganic acids,such as hydrochloric acid or sulfuric acid. On the other hand, if theyhave aromatic OH groups, they can be used in the form of salts withbases, such as alkali phenolates.

The above-described, inventive combinations of compounds of Formula (I)with oxidative hair dye precursors (developer and coupler substances)and/or substantive dyes, are applied in a suitable dye carriercomposition for the dyeing.

Moreover, the dyeing agents may contain other conventional additives,for example, antioxidants such as ascorbic acid, thioglycolic acid orsodium sulfite, as well as perfume oils, penetrants, buffer systems,complexing agents, preservatives, wetting agents, emulsifiers,thickeners and care materials.

The inventive dyeing agent may be prepared in the form of a solution,particularly an aqueous or aqueous-alcoholic solution. However, a cream,a gel or an emulsion is particularly preferred form of preparation.Their composition represents a mixture of dye components with additives,which are customary for such preparations.

Customary additives for solutions, creams, emulsions or gels are, forexample, solvents, such as water, low molecular weight aliphaticalcohols, such as ethanol, propanol or isopropanol, glycerin or glycols,1,2-propylene glycol, moreover, wetting agents or emulsifiers from theclasses of anionic, cationic, amphoteric or nonionic surface activesubstances, such as fatty alcohol sulfates, ethoxylated fatty alcoholsulfates, alkyl sulfonates, alkylbenzenesulfonates,alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols,ethoxylated nonylphenols, fatty acid alkanolamides and ethoxylated fattyesters, furthermore, thickeners, such as higher molecular weight fattyalcohols, starch, cellulose derivatives, petrolatum, paraffin oil andfatty acids, as well as care materials, such as cationic resins, lanolinderivatives, cholesterol, pantothenic acid and betaine. The componentsmentioned are used in amounts customary for such purposes. For example,the wetting agents and emulsifiers are used in concentrations of about0.1 to 30 percent by weight, the thickeners in an amount of about 0.1 to30 percent by weight and the care materials in a concentration of about0.1 to 5.0 percent by weight.

The ready-for-use, inventive dyeing agent is prepared by mixing the dyecarrier compositions with an oxidizing agent directly before use.

As oxidizing agent, mainly hydrogen peroxide or its addition compoundswith urea, melamine, sodium borate or sodium carbonate in the form of a1 to 12 percent, preferably a 3 to 6 percent, aqueous solution come intoconsideration. The ratio by weight of hair dyeing agent to oxidizingagent preferably is about 5:1 to 1:3 and particularly 1:1 to 1:2 here.Larger amounts of oxidizing agents are used especially for higher dyeconcentrations in the hair-dyeing agent or if the hair is to be bleachedmore at the same time. In principle, however, instead of theaforementioned oxidizing agent, it is also possible to use oxygen fromthe air to oxidize the dye.

When the dye carrier composition (the pH of which is about 6 to 11.5) ismixed with the mostly acidic oxidizing agent (the pH of which is about 2to 6.5), the pH of the ready-for-use hair-dyeing agent adjusts itself toa value, which is determined by the amount of alkali in the dye carriercomposition and the amount of acid in the oxidizing agent, as well as bythe mixing ratio. Depending on the composition, the inventive dyeingagent is weakly acidic, neutral or alkaline and, in the ready-for-usestate, has a pH of about 3 to 11 and preferably of about 5 to 10. Theadjustment to a basic pH is made preferably with ammonia. However,organic amines, such as 2-amino-2-methyl-1-propanol,tris(hydroxymethyl)amino-methane, monoethanolamine and triethanolamine,or also inorganic bases, such as sodium hydroxide and potassiumhydroxide may also be used. For adjusting the pH to an acidic range,inorganic or organic acids, such as phosphoric acid, acetic acid, lacticacid, ascorbic acid, citric acid or tartaric acid come intoconsideration.

Subsequently, an amount of this mixture, which depends on the fullnessof the hair, is sufficient to dye it and generally is about 60 to 200gram, is applied on the hair and allowed to act for about 10 to 45minutes and preferably 30 minutes at 10° to 50° C. and preferably at 30°to 40° C., after which the hair is rinsed with water and dried.Optionally, at the end of this rinsing, the hair is washed with ashampoo and possibly given another rinse with a weak organic acid, suchas citric or tartaric acid. Subsequently, the hair is dried.

The inventive hair dyeing agents, which contain diaminopyrazolederivatives of Formula (I) as developer substance, make hair dyeingspossible, with outstanding color fastness, especially as far as thelight fastness, laundering fastness and resistance to crocking areconcerned. With regard to the dyeing characteristics, the inventivedyeing agents, depending on the nature and composition of the dyecomponents, offer a wide palette of different color nuances, whichextend from blond over brown, purple, violet to blue and black colorshades. Pure red shades are also possible. The color shades aredistinguished particularly by their high color intensity. The very gooddyeing properties of the inventive hair dyeing agents are furthermoredistinguished in that they permit tinting of gray, chemically notdamaged hair without any problems and with a good covering power.

The following examples are intended to explain the object of theinvention in greater detail, without limiting it.

EXAMPLES Example 1 Synthesis of 5-Aminomethyl-2H-pyrazole-3,4-diaminesGeneral Procedure A. Synthesis of Ethyl t-Butyl2-(4,5-bis-t-Butoxycarbonylamino-pyrazole-1-yl) Carbonate

4,5-Diamino-1-(2-hydroxyethyl)pyrazole sulfate (9.6 g, 0.04 moles), 11.2mL of triethylamine and 26.3 g (0.12 moles) of di-t-butyl dicarbonatewere dissolved in 500 nL of tetrahydrofuran. The reaction mixture isrefluxed for 58 hours, subsequently cooled and filtered through a layerof SiO₂. The filtrate is then evaporated and the residue chromatographedon SiO₂ with a 1:3 mixture of ethyl acetate and hexane.

Ethyl, t-butyl2-(4,5-bis-t-butoxycarbonylamino-pyrazole-1-yl)(-carbonate) is obtainedin an amount of 8 g (45% of the theoretical).

¹H-NMR (300 MHz, CDCL3): δ=7.76 (br,s, 1H); 6.91 (br,s, 1H); 6.51 (br,s,1H); 4.35 (m, 2H); 4.28 (m, 2H); 1.51-1.47 (m, 27H)

B. Synthesis of t-Butyl[4-t-Butoxycarbonylamino-2-isopropyl-2H-pylazole-3-yl]-carbamate

4,5-Diamino-1-isopropyl-pyrazole sulfate (9.5 g, 0.04 moles) and 17.5 g(0.08 moles) of di-t-butyl dicarbonate are dissolved in a mixture of 50mL of 2N sodium hydrogen carbonate and 120 mL of acetonitrile. Thereaction mixture is stirred for 6 hours, then poured into water andextracted twice with 100 mL of ethyl acetate. The combined extracts areevaporated and the residue taken up in 200 mL of hexane. The precipitateis filtered off and washed with 50 mL of hexane.

t-Butyl[4-t-butoxycarbonylamino-2-isopropyl-ethyl)-2H-pyrazole-3-yl]-carbamateis obtained in an amount of 10 g (73% of the theoretical).

¹H-NMR (300 MHz, CDCL3): δ=7.48 (s, 1H); 6.35 (br,s, 1H); 6.10 (br,s,1H); 4.23 (sp, 1H); 1.50 (s, 9H); 1.49 (s, 9H); 1.44 (d, 6H)

C. Synthesis of t-Butylester of[5-Bromo-4-t-butoxycarbonylamino-2-(2-hydroxyethyl)-2H-pyrazole-3-yl]-carbamate

To a solution of 4.25 g (0.09 moles) of t-butyl2-(4,5-bis-t-butoxycarbonyl-amino-pyrazole-1-yl) carbonate from step A,a solution of 2.13 g of N-bromo-succinimide (0.1 moles) in 40 mL oftetrahydrofuran is added dropwise at room temperature. The reactionmixture is stirred for 3.5 hours at room temperature and then pouredinto a mixture of 100 mL of aqueous Na₂S₂O₃ solution and 100 mL of ethylacetate. The aqueous phrase is extracted with ethyl acetate and thecombined organic phases are then washed with saturated sodium chloridesolution, dried and evaporated. The residue is taken up in a mixture of15 mL of methanol, 50 mL of hexane and 15 mL of water and cooled to 4°C. Subsequently, the reaction mixture is treated in portions with 10equivalents of lithium hydroxide, stirred overnight at room temperatureand then poured into a 1:1 mixture of a 5% aqueous sodium hydrogenphosphate solution and ethyl acetate. The organic phase is dried andevaporated and the residue is chromatographed on silica with a 1:1 to2:1 gradient of ethyl acetate and hexane. t-Butyl[4-t-butoxycarbonylamino-5-bromo-2-isopropyl-2H-pyrazole-3-yl] carbamatewas obtained in a yield of 3.3 g (78% of the theoretical).

¹H-NMR (300 MHz, CDCL3): δ=7.19 (br,s, 1H); 6 (br,s, 1H); 4.12 (m, 2H);3.99 (m, 2H); 2.04 (s, 1H); 1.50 (s, 9H); 1.49 (s, 9H)

D. Synthesis of t-Butyl[4-t-Butoxycarbonylamino-5-bromo-2-isopropyl-2H-pyrazole-3-yl] carbamate

To a solution of 5.5 g (0.016 moles of t-butyl4-t-butoxycarbonyl-amino-2-isopropyl-2H-pyrazole-3-yl carbamate fromstep B, a solution of 3.5 g (0.02 moles) of N-bromo-succinimide in 40 mLof tetrahydrofuran is added at room temperature. The reaction mixture isstirred for 3.5 hours at room temperature and then poured into a mixtureof 100 mL of aqueous Na₂S₂O₃ solution and 100 mL of ethyl acetate. Theaqueous phrase is extracted with ethyl acetate and the combined organicphases are then washed with saturated sodium chloride solution, driedand evaporated. The residue is suspended in a 100 mL of a 1:1 mixture ofdiethyl ether and hexane, filtered and dried. t-Butyl[4-t-butoxycarbonylamino-5-bromo-2-isopropyl-2H-pyrazole-3-yl] carbamateis obtained in a yield of 6 g (89% of the theoretical).

¹H-NMR (300 MHz, CDCL3): δ=6.77 (br,s, 1H); 5.95 (br,s, 1H); 4.46 (sp,1H); 1.50 (s, 9H); 1.49 (s, 9H); 1.44 (d, 6H)

E. Synthesis of t-Butyl[4-t-Butoxycarbonylamino-5-formyl-2-isopropyl-2H-pyrazole-3-yl]carbamate

The t-butyl ester of[4-t-butoxycarbonylamino-5-bromo-2-isopropyl-2H-pyrazole-3-yl] carbamate(3.7 g, 0.01 moles) from step D is dissolved under argon in 100 mL ofanhydrous tetrahydrofuran and 17 mL of a 1.6 M solution of methyllithium in ether (0.03 moles) are added stepwise. The reaction mixtureis cooled to −78° C. and treated stepwise with 7 mL of a 1.5 M solutionof t-butyl lithium (0.01 moles). At the end of the addition, thesolution is stirred for a further 30 minutes at the given temperature.Subsequently, 1.2 g (0.02 moles) of dimethylformamide are added and thereaction mixture stirred for 1 hour at −78° C., allowed to warm upslowly to room temperature, hydrolyzed with water and then poured intodiethyl ether. The aqueous phase is extracted with diethyl ether and thecombined organic phases are then dried with magnesium sulfate. Thesolvent is distilled off on the rotary evaporator and the residuepurified with a 9:1 mixture of petroleum and ethyl acetate on silicagel.

¹H-NMR (300 MHz, CDCL3): δ=9.86 (s, 1H); 7.57 (br,s, 1H); 7.33 (br,s,1H); 4.61 (sp, 1H); 1.50 (s, 9H); 1.49 (s, 9H); 1.47 (d, 6H)

F. Synthesis of t-Butyl[4-t-Butoxycarbonylamino-5-formyl-2-(2-hydroxyethyl)-2H-pyrazole-3-yl]-carbamate

The t-butyl ester of[5-bromo-4-t-butoxycarbonylamino-2-(2-hydroxyethyl)-2H-pyrazole-3-yl]carbamate (4.21 g, 0.01 moles) from step C. is dissolved under argon in100 mL of anhydrous tetrahydrofuran and 17 mL of a 1.6 M solution ofmethyl lithium in ether (0.03 moles) are added stepwise. The reactionmixture is cooled to −78° C. and treated stepwise with 7 mL of 1.5 Msolution of t-butyl lithium (0.01 moles). At the end of the addition,the solution is stirred for a further 30 minutes at the giventemperature. Subsequently, 1.2 g (0.02 moles) of dimethylformamide areadded and the reaction mixture stirred for 1 hour at −78° C., allowed towarm up slowly to room temperature, hydrolyzed with water and thenpoured into diethyl ether. The aqueous phase is extracted with diethylether and the combined organic phases are then dried with magnesiumsulfate. The solvent is distilled off on the rotary evaporator and theresidue purified with a 9:1 mixture of petroleum and ethyl acetate onsilica gel.

¹H-NMR (300 MHz, CDCL3): δ=9.86 (s, 1H); 7.6 (br,s, 2H); 4.29 (m, 2H);4.10 (m, 2H); 1.50 (s, 9H); 1.50 (s, 9H); 1.48 (d, 6H)

G. Synthesis of 5-Aminomethyl-2H-pyrazole-3,4-diamines

The aldehyde derivatives (0.0001 moles) from step E or F and 0.00015moles of the corresponding amine are dissolved in 1,2-dichloroethane.Subsequently 0.1 mL of an acetic acid solution (1 M in1,2-dichloroethane) and 0.06 g of NaBH(OAc)₃ (0.0003 moles) are addedand the reaction mixture is stirred 5 to 15 hours at room temperature.At the end of the reaction, the reaction mixture is poured into 10 mL ofethyl acetate and the organic phase is extracted with sodium hydrogencarbonate and then dried with magnesium sulfate. The solvent isevaporated in a rotary evaporator and the residue purified on silica gelwith a 9:1 mixture of petroleum ether and ethyl acetate. The product, soobtained, is heated in 4 mL of ethanol to 50° C. Subsequently, for thepreparation of the hydrochloride, 1.5 mL of a 2.9 M ethanolic solutionof hydrochloric acid is added dropwise. The precipitate is filtered off,washed twice with I mL of methanol and then dried.

a.4-{[4,5-Diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol*HCl

Aldehyde derivative used: of Step F

Amine used: 4-amino-phenol

Mass spectrum: MH⁺ 264 (100)

b.2-{4,5-Diamino-3-[(4-amino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol*HCl

Aldehyde derivative used: of Step F

Amine used: 1,4-diaminobenzene

Mass spectrum: MH⁺ 263 (100)

c. 2-(4,5-Diamino-3-phenylaminomethyl-pyirazole-1-yl)-ethanol*HCl

Aldehyde derivative used: of Step F

Amine used: 1,3-diaminobenzene

Mass spectrum: MH⁺ 248 (100)

d. 2-Isopropyl-5-phenylaminomethyl-2H-pyrazole-3,4-diamine*HCl

Aldehyde derivative used: of Step F

Amine used: aniline

Mass spectrum: MH⁺ 246 (100)

e.2-{4,5-Diamino-3-[(3-amino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol*HCl

Aldehyde derivative used: of Step F

Amine used: 1,3-diaminobenzene

Mass spectrum: MH⁺ 263 (100)

f.2-{4,5-Diamino-3-[(4-amino-2-methyl-phenylamino)-methyl]-pyrazole-1-yl}-ethanol*HCland2-{4,5-diamino-3-[(4-amino-3-methyl-phenylamino)-methyl]-pyrazole-1-yl}-ethanol*HCl

Aldehyde derivative used: of Step F

Amine used: 2,5-diamino-toluene

Mass spectrum: MH⁺ 277 (100)

g.2-(4,5-Diamino-3-{[4-amino-2-(2-hydroxyethyl)-phenylamino]-methyl}-pyrazole-1-yl)-ethanol*HCland2-(4,5-diamino-3-{[4-amino-3-(2-hydroxyethyl)-phenylamino]-methyl}-pyrazole-1-yl)-ethanol*HCl

Aldehyde derivative used: of Step F

Amine used: 2-(2,5-diamino-phenyl)-ethanol

Mass spectrum: MH⁺ 307 (100)

h.2-{4,5-Diamino-3-[(4-dimethylamino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol*HCl

Aldehyde derivative used: of Step F

Amine used: 4-dimethylamino-aniline

Mass spectrum: MH⁺ 291 (100)

i.2-[4,5-Diamino-3-(benzo[1,3]dioxol-5-ylaminomethyl)-pyrazole-1-yl]-ethanol*HCl

Aidehyde derivative used: of Step F

Amine used: benzo[1,3]dioxol-5-ylamine

Mass spectrum: MH⁺ 292 (100)

j.4-Chloro-2-{[4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}phenol*HCl

Aldehyde derivative used: of Step F

Amine used: 2-amino-4-chloro-phenol

Mass spectrum: MH⁺ 297 (100)

k.3-{[4,5-Diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}phenol*HCl

Aldehyde derivative used: of Step F

Amine used: 3-amino-phenol

Mass spectrum: MH⁺ (100)

l.5-{[4,5-Diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}2-methyl-phenol*HCl

Aldehyde derivative used: of Step F

Amine used: 5-amino-2-methyl-phenol

Mass spectrum: MH⁺ 264 (100)

m.2-{4,5-Diamino-3-[(3,4-dimethoxy-phenylamino)-methyl]-pyrazole-1-yl}-ethanol*HCl

Aldehyde derivative used: of Step F

Amine used: 3,4-dimethoxy-aniline

Mass spectrum: MH⁺ 308 (100)

n.2-{[4,5-Diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}-4-nitrophenol*HCl

Aldehyde derivative used: of Step F

Amine used: 2-amino-4-nitro-phenol

Mass spectrum: MH⁺ 309 (100)

o. 4-[(4,5-Diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenol*HCl

Aldehyde derivative used: of Step E

Amine used: 4-amino-phenol

Mass spectrum: MIH⁺ 262 (100)

p. 3-[(4,5-Diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenol*HCl

Aldehyde derivative used: of Step E

Amine used: 3-amino-phenol

Mass spectrum: MH⁺ 262 (100)

q.5-[(4,5-Diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-2-methyl-phenol*HCl

Aldehyde derivative used: of Step E

Amine used: 5-amino-2-methyl-phenol

Mass spectrum: MH⁺ (100)

r.5-[(3,4-Dimethoxy-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine*HCl

Aldehyde derivative used: of Step E

Amine used: 3,4-dimethoxy-aniline

Mass spectrum: MH⁺ 306 (100)

s.2-[(4,5-Diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-4-nitro-phenol*HCl

Aldehyde derivative used: of Step E

Amine used: 2-arnino-4-nitro-phenol

Mass spectrum: MH⁺ 306 (40)

t.5-[(3-Amino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine*HCl

Aldehyde derivative used: of Step E

Amine used: 1,3-diaminobenzene

Mass spectrum: MH⁺ 261 (100)

u.5-[(4-Amino-phenylamino)-methyl]-2-isopropyl-2H-prazole-3,4-diamine*HCl

Aldehyde derivative used: of Step E

Amine used: 1,4-diaminobenzene

Mass spectrum: MH⁺ 261 (100)

v.5-[(4-Amino-2-methyl-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine*HCland5-[(4-amino-3-methyl-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine*HCl

Aldehyde derivative used: of Step E

Amine used: 2,5-diamino-toluene

Mass spectrum: MH⁺ 275 (100)

w.2-{5-Amino-2-[(4,5-diamino-1-isopropyl-1H-prazole-3-ylmethyl)-amino]-phenyl}-ethanol*HCland2-{6-amino-3-[(4,5-diamino-1-isopropyl-1H-prazole-3-ylmethyl)-amino]-phenyl}-ethanol*HCl

Aldehyde derivative used: of Step E

Amine used: 2-(2,5-diamino-phenyl)-ethanol

Mass spectrum: MH⁺ 305 (100)

x.2-{4-Amino-2-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenoxy}-ethanol*HCl

Aldehyde derivative used: of Step E

Amine used: 2-(2,4-diamino-phenoxy)-ethanol

Mass spectrum: MH⁺ 321 (100)

y.5-[(4-Dimethylamino-phenylamino)methyl]-2-isopropyl-2H-pyrazole-3,4-diamine*HCl

Aldehyde derivative used: of Step E

Amine used: 4-dimethylamino-aniline

Mass spectrum: MH⁺ 289 (100)

Examples 2 to 26 Hair Dyeing Agent

Hair dye solutions of the following composition are prepared:

1.25 mmoles developer substance of Formula (I) of Table 1 1.25 mmolescoupler substance of Table 1 1.0 g potassium oleate (8% aqueoussolution) 1.0 g ammonia (22% aqueous solution) 1.0 g ethanol 0.3 gascorbic acid ad 100.0 g water

The above dye solution (50 g) is mixed immediately before use with 50 gof a 6% aqueous hydrogen peroxide solution. Subsequently, the mixture isapplied on bleached hair. After a period of action of 30 minutes at 40°C., the hair is rinsed with water, washed with a conventional shampooand dried. The resulting dyeings are summarized in Table 1.

TABLE 1 Coupler Substance II. I. 1,3-diamino- Developer 3-amino- 4-Substance 2-chloro- (2-hydroxy- III. of 6- ethoxy)- 5-amino- ExampleFormula methyl- benzene 2-methyl- IV. No. (I) phenol sulfate phenol1-naphthol 2. of red violet orange light Example orange 1a 3. of violetblue claret gray red Example 1b 4. of violet blue red orange Exampleviolet 1c 5. of violet blue red orange Example violet 1d 6. of violetblue claret gray red Example 1e 7. of violet blue claret gray redExample 1f 8. of violet blue claret gray red Example 1g 9. of lightlight claret gray red Example violet blue 1h 10. of violet blue redorange Example violet 1i 11. of light light claret gray red Exampleviolet blue 1j 12. of light light claret gray red Example violet blue 1k13. of light light claret gray red Example violet blue 1l 14. of lightlight red gray red Example violet blue 1m 15. of red brown orange orangeExample 1n 16. of red violet orange light Example orange 1o 17. ofviolet violet claret orange Example blue 1p 18. of light light claretorange Example violet blue 1q 19. of light light claret orange Exampleviolet blue 1r 20. of light light claret orange Example violet blue 1s21. of light light claret orange Example violet blue 1t 22. of violetblue light Gray Example violet 1u 23. of violet blue light gray Exampleviolet 1v 24. of violet blue light gray Example violet 1w 25. of lightlight light gray Example violet blue violet 1x 26. of light light lightgray Example violet blue violet 1y

Examples 27 to 38 Hair Dyeing Agent

Hair dyeing solutions of the following composition are prepared:

X g developer E1 to E2 of Formula (I) of Table 2 U g developer E8 to E15of Table 2 Y g coupler substance K11 to K36 of Table 4 10.0 g potassiumoleate (8% aqueous solution) 10.0 g ammonia (22% aqueous solution) 10.0g ethanol 0.3 g ascorbic acid ad 100.0 g water

The above dye solution (30 g) is mixed immediately before use with 30 gof a 6% aqueous hydrogen peroxide solution. Subsequently, the mixture isapplied on bleached hair. After a period of action of 30 minutes at 40°C., the hair is rinsed with water, washed with a conventional shampooand dried. The resulting dyeings are summarized in Table 5.

Examples 39 to 50 Hair Dyeing Agent

Creamy dye carrier compositions with the following components areprepared:

X g developer substance E3 to E6 of Formula (I) of Table 2 U g developersubstance E8 to E15 of Table 2 Y g coupler substance K11 to K36 of Table4 Z g direct dye D2 of Table 3 15.0 g cetyl alcohol 0.3 g ascorbic acid3.5 g sodium lauryl alcohol diglycol ether sulfate, 28% aqueous solution3.0 g ammonia, 22% aqueous solution 0.3 g sodium sulfite, water-free ad100.0 g water

The above dye cream (30 g) is mixed immediately before use with 30 g ofa 6% aqueous hydrogen peroxide solution. Subsequently, the mixture isapplied on bleached hair. After a period of action of 30 minutes at 40°C., the hair is rinsed with water, washed with a conventional shampooand dried. The resulting dyeings are summarized in Table 6.

TABLE 2 Developer Substance E14-{[4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol*HCl E24-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]- phenol*HClE3 2-{4,5-diamino-3-[(4-amino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol*HCl E45-[(4-amino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine*HCl E52-isopropyl-5-phenylaminomethyl-2H-pyrazole-3,4-diamine*HCl E62-(4,5-diamino-3-phenylaminomethyl-pyrazole-1-yl)-ethanol*HCl E81,4-diaminobenzene E9 2,5-diamino-phenylethanol sulfate E103-methyl-4-amino-phenol E11 4-amino-2-aminomethyl-phenol-dihydrochlorideE12 4-amino-phenol E13 N,N-bis(2′-hydroxyethyl)-p-phenylenediaminesulfate E14 4,5-diamino-1-(2′-hydroxyethyl)-pyrazole sulfate E152,5-diaminotoluene sulfate

TABLE 3 Substantive Dyes D1 2,6-diamino-3-((pyridine-3-yl)azo)pyridineD2 6-chloro-2-ethylamino-4-nitrophenol D3 2-amino-6-chloro-4-nitrophenol

TABLE 4 Coupler Substances K11 1,3-diaminobenzene K122-amino-4-(2′-hydroxyethyl)amino-anisole sulfate K131,3-diamino-4-(2′-hydroxyethoxy)benzene sulfate K142,4-diamino-5-fluoro-toluene sulfate K153-amino-2-methylamino-6-methoxy-pyridine K163,5-diamino-2,6-dimethoxy-pyridine-dihydrochloride K172,4-diamino-5-ethoxy-toluene sulfate K18 N-(3-dimethylamino)phenylureaK19 1,3-bis(2,4-diaminophenoxy)propane-tetrahydrochloride K213-amino-phenol K22 5-amino-2-methyl-phenol K233-amino-2-chloro-6-methyl-phenol K24 5-amino-4-fluoro-2-methyl-phenolsulfate K25 1-naphthol K26 1-acetoxy-2-methyl-naphthalene K311,3-dihydroxy-benzene K32 2-methyl-1,3-dihydroxy-benzene K331-chloro-2,4-dihydroxy-benzene K344-(2′-hydroxyethyl)amino-1,2-methylenedioxybenzene hydro- chloride K353,4-methylenedioxy-phenol K36 2-amino-5-methyl-phenol

TABLE 5 Hair-Dyeing Agents Example No. 27 28 29 30 Dye (amount of dye ingrams) E1 0.30 0.30 0.30 0.30 E8 0.25 E13 0.20 E14 0.30 E15 0.20 0.30K22 0.30 0.30 0.30 K23 0.35 K31 0.18 0.20 K32 0.22 K33 0.20 Dyeingreddish reddish reddish reddish Result brown brown brown brown ExampleNo. 31 32 33 34 Dye (amount of dye in grams) E1 0.15 0.20 0.10 0.30 E80.25 E10 0.15 E11 0.10 E12 0.20 E13 0.20 E14 0.30 E15 0.20 0.30 K22 0.200.10 0.20 0.15 K23 0.10 0.15 K25 0.10 0.10 K26 0.15 K31 0.18 0.20 K320.22 K33 0.20 Dyeing reddish reddish reddish reddish Result brown brownbrown brown Example No. 35 36 37 38 Dye (amount of dye in grams) E2 0.300.30 0.30 0.30 E8 0.25 E13 0.20 E14 0.30 E15 0.20 0.30 K22 0.30 0.300.30 K23 0.35 K31 0.18 0.20 K32 0.22 K33 0.20 Dyeing reddish reddishreddish reddish Result brown brown brown brown

TABLE 6 Hair Dyeing Agents Example No. 39 40 41 42 43 44 Dye (amount ofdye in grams) E3 0.20 0.30 0.20 E4 0.25 0.20 E5 0.20 E6 0.20 E8 1.60 E131.80 E15 1.60 0.50 0.50 0.50 K12 0.10 0.10 0.10 K13 1.10 1.10 1.10 K230.05 0.10 0.10 0.10 K31 1.10 1.10 1.10 0.40 0.40 0.40 D2 0.10 0.10 0.10Dyeing black black black brown brown brown Result Example No. 45 46 4748 49 50 Dye (amount of dye in grams) E3 0.20 0.30 E4 0.20 0.20 E5 0.20E6 0.30 E15 1.80 1.80 1.80 0.30 0.50 0.60 K12 0.10 0.10 0.10 K13 1.101.10 1.10 K23 0.05 0.10 0.10 0.10 K31 1.10 1.10 1.10 0.40 0.40 0.40 D20.10 0.10 0.10 Dyeing black black black brown brown brown Result

Unless stated otherwise, all percentages in the present application arepercentages by weight.

What is claimed is:
 1. Diaminiopyrazole derivative of the generalFormula (I) or its physiological tolerated, water-soluble salt withinorganic or organic acids

wherein R1 represents a C₁-C₆ alkyl group, a C₂-C₄ hydroxyalkyl group, aC₃-C₄ dihydroxyalkyl group or a C₂-C₆ alkoxy (C₁-C₂) alkyl group, aphenyl group, a benzyl group or a substituted benzyl group; R2 and R3independently of one another are hydrogen, a C₁-C₆ alkyl group, ahydroxy (C₂-C₄) alkyl group, a dihydroxy (C₃-C₄) alkyl group or a C₂-C₄alkoxy-(C₁-C₂) alkyl group or R2 and R3, together with the nitrogen,form a 4-member to 8-member heteroaliphatic ring; R4 represents hydrogenor a C₁-C₆ alkyl group; R5 is hydrogen, a C₁-C₆ alkyl group, anunsaturated C₂-C₆ alkyl group, a hydroxy (C₂-C₄) alkyl group, adihydroxy (C₃-C₄) alkyl group, an amino (C₂-C₄) alkyl group, adimethylamino (C₂-C₄) alkyl group, an acetylamino (C₂-C₄) alkyl group, amethoxy (C₂-C₄) alkyl group, an ethoxy (C₂-C₄) alkyl group, a C₁-C4cyanoalkyl group, a carboxy (C₁-C₄) alkyl group or an aminocarbonyl(C₁-C₄) alkyl group; R6, R7, R8, R9, R10 independently of one anotherrepresent hydrogen, a halogen atom (F, Cl Br, I), a cyano group, ahydroxy group, a C₁-C₄ alkoxy group, a hydroxy (C₂-C₄) alkoxy group, aC₁-C₆ alkyl group, a C₁-C₄ alkylthioether group, a mercapto group, anitro group, an amino group, a (C₁-C₄) alkylamino group, a hydroxy(C₂-C₄) alkylamino group, a di(C₁-C₄) alkylamino group, adi(hydroxy(C₂-C₄)alkyl) amino group, a (dihydroxy(C₃-C₄)alkyl) aminogroup, a (hydroxy(C₂-C₄)alkyl)-(C₁-C₄)alkylamino group, atrifluoromethyl group, a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃group, an —Si(CH₃)₃ group, a hydroxy(C₂-C₄) alkyl group or adihydroxy(C₃-C₄) alkyl group or two adjacent R6 to R10 groups form an—O—CH2—O—bond.
 2. The diaminopyrazole derivative of claim 1, wherein R2and R3 in Formula (I) represent hydrogen and R1 is a C₁-C₄ alkyl group,a C₂-C₄ hydroxyalkyl group, a benzyl group or a methylbenzyl group. 3.The diaminopyrazole derivative of claim 1, wherein R2, R3, R4 and R5 inFormula (I) are hydrogen and R1 is a C₁-C₄ alkyl group, a C₂-C₄hydroxyalkyl group, a benzyl group or a methylbenzyl group.
 4. Thediaminopyrazole derivative of claim 1, wherein R2, R3, R4 and R5 inFormula (I) are hydrogen and R1 is a C₁-C₄ alkyl group, a C₂-C₄hydroxyalkyl group, a benzyl group or a methylbenzyl group, and at leastone of the R6 to R10 groups is a hydroxy group or an amino group, whilethe remaining R6 to R10 groups are hydrogen.
 5. The diaminopyrazolederivative of claim 1, wherein it is selected from4-{[4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol,2-{4,5-diamino-3-[(4-amino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-(4,5-diamino-3-phenylaminomethyl-pyrazole-1-yl)-ethanol,2-isopropyl-5-phenylaminomethyl-2H-pyrazole-3,4-diamine,2-{4,5-diamino-3-[(3-amino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-{4,5-diamino-3-[(4-amino-2-methyl-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-{4,5-diamino-3-[(4-amino-3-methyl-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-(4,5-diamino-3-{[4-amino-2-(2-hydroxyethyl)-phenylamino]-methyl}-pyrazole-1-yl)-ethanol,2-(4,5-diamino-3-{[4-amino-3-(2-hydroxyethyl)-phenylamino]-methyl}-pyrazole-1-yl)-ethanol,2-{4,5-diamino-3-[(4-dimethylamino-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-[4,5-diamino-3-(benzo[1,3]dioxol-5-ylaminomethyl)-pyrazole-1-yl]-ethanol,4-chloro-2-{[4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol,3-{[4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}-phenol,5-{[4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole-3-ylmethyl]-amino}-2-methyl-phenol,2-{4,5-diamino-3-[(3,4-dimethoxy-phenylamino)-methyl]-pyrazole-1-yl}-ethanol,2-{[4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole-3-ylmethyl]-amino}-4-nitro-phenol,4-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenol,3-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenol,5-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-2-methyl-phenol,5-[(3,4-dimethoxy-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,2-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-4-nitro-phenol,5-[(3-amino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,5-[(4-amino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,5-[(4-amino-2-methyl-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,5-[(4-amino-3-methyl-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine,2-{5-amino-2-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenyl}-ethanol,2-{6-amino-3-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenyl}-ethanol,2-{4-amino-2-[(4,5-diamino-1-isopropyl-1H-pyrazole-3-ylmethyl)-amino]-phenoxy}-ethanoland5-[(4-dimethylamino-phenylamino)-methyl]-2-isopropyl-2H-pyrazole-3,4-diamine.6. An agent for the oxidative dyeing of keratin fibers on the basis of acombination of a developer substance and a coupler substance, wherein itcontains at least one diaminopyrazole derivative of Formula (I) of claim1 as developer substance.
 7. The agent of claim 6, wherein thediaminopyrazole derivative of Formula (I) is contained in an amount of0.005 to 20 percent by weight.
 8. The agent of claim 6, wherein thecoupler substance is selected from N-(3-dimethylamino-phenyl)-urea,2,6-diamino-pyridine, 2-amino-4-[(2-hydroxyethyl)-amino]-anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxy-ethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxy-pyridine,3-amino-6-methoxy-2-(methylamino)-pyridine,2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene,2,4-diamino-1-(3-hydroxy-propoxy)-benzene,2,4-diamino-1-(3-methoxypropoxy)-benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[(di(s-hydroxy-ethyl)amino]-aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline,3-[(2-aminoethyl)-amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane,di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole,3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol,5-amino-4-fluoro-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol,5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichloro-phenol,3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol,3-amino-phenol, 2-[(3-hydroxyphenyl)-amino]-acetamide,5-[(2-hydroxy-ethyl)amino]-2-methyl-phenol,3-[(2-hydroxy-ethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol,5-amino-2-ethyl-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol,5-[(3-hydroxypropyl)amino]-2-methyl-phenol,3-[(2,3-dihydroxypropyl)-amino]-2-methyl-phenol,3-[(2-hydroxyethyl)-amino]-2-methyl-phenol, 2-amino-3-hydroxy-pyridine,5-amino-4-chloro-2-methyl-phenol, 1-naphthol, 1,5-dihydroxy-naphthalene,1,7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene,2,7-dihydroxy-naphthalene, 2-methyl-1-naphthol-acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,1,3-dihydroxy-2,4-dimethylbenzene, 3,4-methylenedioxy-phenol,3,4-methylenedioxy-aniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxol,6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diamino-benzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 4-hydroxy-indole,5-hydroxy-indole, 6-hydroxy-indole, 7-hydroxy-indole and2,3-indolindione, or their salts.
 9. The agent of claim 6, wherein itcontains additionally at least one further developer substance and/or atleast one substantive dye.
 10. The agent of claim 6, wherein the dyecarrier composition is mixed with the oxidizing agent in a ratio byweight of 5:1 to 1:3.
 11. The agent of claim 10, wherein theready-for-use oxidation dyeing agent has a pH of 3 to
 11. 12. The agentof claim 6, wherein it is a hair-dyeing agent.